CN109385189A - Electroconductive polymer dispersion liquid, conductive membrane and its manufacturing method and antistatic property container and its manufacturing method - Google Patents

Electroconductive polymer dispersion liquid, conductive membrane and its manufacturing method and antistatic property container and its manufacturing method Download PDF

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Publication number
CN109385189A
CN109385189A CN201810885353.2A CN201810885353A CN109385189A CN 109385189 A CN109385189 A CN 109385189A CN 201810885353 A CN201810885353 A CN 201810885353A CN 109385189 A CN109385189 A CN 109385189A
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China
Prior art keywords
electroconductive polymer
dispersion liquid
polymer dispersion
conductive membrane
ethylene carbonate
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CN201810885353.2A
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Chinese (zh)
Inventor
松林总
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Shin Etsu Polymer Co Ltd
Shin Etsu Chemical Co Ltd
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Shin Etsu Polymer Co Ltd
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Publication of CN109385189A publication Critical patent/CN109385189A/en
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y10T428/1393—Multilayer [continuous layer]

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Abstract

Electroconductive polymer dispersion liquid of the invention contains: the conductive composite body comprising pi-conjugated electroconductive polymer and polyanion, tertiary ethylene carbonate polymer and decentralized medium.

Description

Electroconductive polymer dispersion liquid, conductive membrane and its manufacturing method and antistatic Property container and its manufacturing method
Technical field
The present invention relates to a kind of electroconductive polymer dispersion liquid containing pi-conjugated electroconductive polymer, conductive membrane and Its manufacturing method, antistatic property container and its manufacturing method.
This application claims the priority based on the application " Patent 2017-153567 " submitted in Japan on the 8th of August in 2017, this In quote its content.
Background technique
It is formed with the conductor of conductive layer on the surface of plastic basis material, for requiring antistatic purposes, such as electronic component Packaging or container, the packaging of food or container etc..
As the conductive material that aforesaid conductive layer is included, due to electric conductivity and transparent excellent and electric conductivity independent of Humidity and stablize, sometimes use pi-conjugated electroconductive polymer.
It as the forming method of the conductive layer containing pi-conjugated electroconductive polymer, such as can enumerate: pi-conjugated electric conductivity will be contained The electroconductive polymer dispersed liquid coating that the conductive composite body of macromolecule and polyanion is dispersed in water is allowed in substrate Dry method (patent document 1).
Existing technical literature
Patent document
Patent document 1: International Publication WO2015/108001
Summary of the invention
Problems to be solved by the invention
In general, plastic basis material is hydrophobicity, hydrophily is low.Therefore, disclosed in Patent Document 1 that water-based electric conductivity is high There is the tendency low to the adhesiveness of substrate coated on the conductive layer that plastic basis material is formed in molecular dispersions.It is used among plastics In the case that the high polyolefin of hydrophobicity is as substrate, the conductive layer formed by water-based electroconductive polymer dispersion liquid is to substrate Adhesiveness it is especially low.
In addition, the hydrophily due to the conductive layer formed by water-based electroconductive polymer dispersion liquid is high, there are water resistances Low tendency, needs to be improved water resistance.
The object of the present invention is to provide a kind of electroconductive polymer dispersion liquids, can be readily formed and glue to plastic basis material The conductive layer of conjunction property and excellent water resistance.In addition, the object of the invention is also to provide a kind of with to plastic film substrate The conductive membrane and its manufacturing method and antistatic property container of adhesiveness and the conductive layer of excellent water resistance and its manufacturer Method.
A technical solution to solve project
The present invention includes following manner.
[1] a kind of electroconductive polymer dispersion liquid, contains:
Conductive composite body, it includes pi-conjugated electroconductive polymer and polyanions；
Tertiary ethylene carbonate polymer；And
Decentralized medium.
[2] the electroconductive polymer dispersion liquid according to [1], wherein
The tertiary ethylene carbonate polymer includes from the monomeric unit of tertiary ethylene carbonate and from vinyl acetate The monomeric unit of ester.
[3] the electroconductive polymer dispersion liquid according to [1] or [2], wherein
The pH according to JIS Z 8802:2011 measurement of the tertiary ethylene carbonate polymer is 4~9.
[4] the electroconductive polymer dispersion liquid according to any one of [1]~[3], wherein
The decentralized medium contains water.
[5] the electroconductive polymer dispersion liquid according to any one of [1]~[4], wherein
The pi-conjugated electroconductive polymer is poly- (3,4- ethyldioxythiophene).
[6] the electroconductive polymer dispersion liquid according to any one of [1]~[5], wherein
The polyanion is polystyrolsulfon acid.
[7] the electroconductive polymer dispersion liquid according to any one of [1]~[6], wherein
The electroconductive polymer dispersion liquid also contains adhesive ingredients.
[8] the electroconductive polymer dispersion liquid according to [7], wherein
Described adhesive ingredient is polyester resin.
[9] the electroconductive polymer dispersion liquid according to [7], wherein
Described adhesive ingredient is the acrylic resin containing glycidyl.
[10] a kind of conductive membrane, has:
Film substrate；And
What the electroconductive polymer dispersion liquid as described in any one of [1]~[9] was formed on the surface of the film substrate leads Electric layer.
[11] conductive membrane according to [10], wherein
The film substrate includes polyolefin-based resins.
[12] conductive membrane according to [11], wherein
The polyolefin-based resins are acrylic resin.
[13] a kind of manufacturing method of conductive membrane comprising [1]~[9] are applied on an at least side surface for film substrate Any one of described in electroconductive polymer dispersion liquid, be allowed to the dry process for forming conductive layer.
[14] manufacturing method of the conductive membrane according to [13], wherein
The film substrate includes polyolefin-based resins.
[15] manufacturing method of the conductive membrane according to [14], wherein
The polyolefin-based resins are acrylic resin.
[16] manufacturing method of the conductive membrane according to any one of [13]~[15], wherein
The film substrate has hydrophilic radical on the surface.
[17] manufacturing method of the conductive membrane according to [16], wherein
The film substrate is obtained and carrying out Corona discharge Treatment to surface.
[18] a kind of antistatic property container, it includes obtain the forming of conductive membrane described in any one of [10]~[12] Formed body.
[19] a kind of manufacturing method of antistatic property container, includes
The process of the manufacturing method manufacture conductive membrane of the conductive membrane according to any one of [13]~[17]；And
Make the process of the conductive membrane forming.
[20] manufacturing method of the antistatic property container according to [19], wherein
The process for shaping conductive membrane makes the vacuum-formed process of the conductive membrane.
Invention effect
Electroconductive polymer dispersion liquid through the invention can be readily formed adhesiveness and water resistance to plastic basis material Excellent conductive layer.
Conductive membrane of the invention has to the adhesiveness of plastic film substrate and the conductive layer of excellent water resistance.
Said conductive film can be easily manufactured in the manufacturing method of conductive membrane through the invention.
Antistatic property container of the invention has to the adhesiveness of plastic film substrate and the conductive layer of excellent water resistance.
Aforementioned antistatic property container can be easily manufactured in the manufacturing method of antistatic property container through the invention.
Detailed description of the invention
Fig. 1 is the cross-sectional view for indicating an example of conductive membrane of the invention.
Fig. 2 is the cross-sectional view for indicating an example of antistatic property container of the invention.
Specific embodiment
< electroconductive polymer dispersion liquid >
The electroconductive polymer dispersion liquid of one embodiment of the present invention contain conductive composite body, tertiary ethylene carbonate polymer, And decentralized medium.
(conductive composite body)
Conductive composite body in the method includes pi-conjugated electroconductive polymer and the polyanion with anionic group.By It is coordinated in aforementioned polyanion and aforementioned pi-conjugated electroconductive polymer, the anionic group of polyanion is doped to pi-conjugated conduction Property macromolecule in, therefore form conductive conductive composite body.
In polyanion, and not all anionic group is all doped in pi-conjugated electroconductive polymer, also has remaining yin Ionic group.Since remaining anionic group is hydrophilic radical, conductive composite body has water dispersible.
[pi-conjugated electroconductive polymer]
As pi-conjugated electroconductive polymer, as long as organic polymer that main chain is made of pi-conjugated system and having of the invention Effect is not particularly limited, such as can enumerate: multi-metal polypyrrole electroconductive polymer, gathers polythiophene class electroconductive polymer Acetylene class electroconductive polymer, polyhenylene class electroconductive polymer, polyphenylene vinylene class electroconductive polymer, polyaniline compound are led Electrical macromolecule, polyacene class electroconductive polymer, Polythienylenevinylethermoelectric class electroconductive polymer and their copolymer Deng.From the viewpoint of aerial stability, preferably multi-metal polypyrrole electroconductive polymer, polythiophene class and polyaniline compound Electroconductive polymer, from the viewpoint of the transparency, more preferable polythiophene class electroconductive polymer.
As polythiophene class electroconductive polymer, can enumerate: polythiophene, poly- (3 methyl thiophene), poly- (3- ethylthiophene), Poly- (3- propyl thiophene), poly- (3- butyl thiophene), poly- (3- heptyl thiophene), poly- (3- octyl thiophene), gather poly- (3- hexyl thiophene) (3- decylthiophene), poly- (3- dodecylthiophene), poly- (3- octadecyl thiophene), poly- (3 bromo thiophene), poly- (3- chlorothiophene), Poly- (3- iodothiophen), poly- (3- cyano thiophene), poly- (3- tolylthiophene), poly- (3,4- thioxene), poly- (3,4- dibutyl thiophene Pheno), poly- (3- hydroxy thiophene), poly- (3- methoxythiophene), poly- (3- ethoxythiophene), poly- (3- butoxy thiophene), it is poly- (3- oneself Oxygroup thiophene), poly- (3- oxygroup in heptan thiophene), poly- (3- octyloxy thiophene), poly- (3- decyloxy thiophene), poly- (3- dodecyloxy Thiophene), poly- (3- octadecane epoxide thiophene), poly- (3,4- dihydroxy thiophene), poly- (3,4- dimethoxy-thiophene), poly- (3,4- bis- Ethoxythiophene), poly- (3,4- dipropoxy thiophene), poly- (3,4- dibutoxy thiophene), poly- (bis- hexyloxy thiophene of 3,4-), poly- (3,4- oxygroup thiophene in bis- heptan), poly- (bis- octyloxy thiophene of 3,4-), poly- (bis- decyloxy thiophene of 3,4-), poly- (bis- (dodecane of 3,4- Oxygroup) thiophene), poly- (3,4- ethyldioxythiophene), poly- (3,4- popylenedioxythiphene), poly- (3,4- butylidene dioxy thiophene Pheno), poly- (3- methyl -4- methoxythiophene), poly- (3- methyl -4- ethoxythiophene), poly- (3- carboxy thiophene), poly- (3- methyl - 4- carboxy thiophene), poly- (3- methyl -4- carboxyethyl thiophene), poly- (3- methyl -4- carboxylic butyl thiophene).
As multi-metal polypyrrole electroconductive polymer, can enumerate: polypyrrole, poly- (3- methylpyrrole), gathers poly- (N- methylpyrrole) (3- N-ethyl pyrrole N), poly- (3- n-propyl pyrroles), poly- (3- octyl pyrroles), poly- (3- decyl pyrroles), gather poly- (3- butyl pyrroles) (3- dodecyl pyrroles), poly- (3,4- dimethyl pyrrole), poly- (3,4- dibutyl pyrroles), poly- (3- carboxy pyrrole), poly- (3- first Base -4- carboxy pyrrole), poly- (3- methyl -4- carboxyethyl pyrroles), poly- (3- methyl -4- carboxylic butyl pyrroles), poly- (3- hydroxyl pyrrole Cough up), poly- (3- methoxypyrrole), poly- (3- ethyoxyl pyrroles), poly- (3- butoxy pyrroles), poly- (3- hexyloxy pyrroles), poly- (3- Methyl -4- hexyloxy pyrroles).
As polyaniline compound electroconductive polymer, can enumerate: polyaniline, poly- (3- isobutyl-aniline), gathers poly- (2-aminotoluene) (2- anilinesulfonic acid), poly- (3- anilinesulfonic acid).
It is particularly preferably poly- from the viewpoint of electric conductivity, the transparency, heat resistance among aforementioned pi-conjugated electroconductive polymer (3,4- ethyldioxythiophene).
The pi-conjugated electroconductive polymer that conductive composite body is included can be a kind, can also be two or more.
[polyanion]
Polyanion refers to polymer in the molecule with 2 or more monomeric units with anionic group.The poly- yin The anionic group of ion plays pi-conjugated electroconductive polymer the function as dopant, makes pi-conjugated electroconductive polymer Electric conductivity enhancing.
As the anionic group of polyanion, preferably sulfonic group or carboxyl.
As the concrete example of such polyanion, can enumerate: polystyrolsulfon acid, polyvinylsulfonic acid, polyallyl sulfonic acid, Containing sulfonic acrylic polymer, contain sulfonic methacrylic polymer, poly- (2- acrylamide -2- methyl-prop Sulfonic acid), polyisoprene sulfonic acid, polymethylacrylic acid Sulfoethyl esters, poly- (methacrylic acid -4- sulfo group butyl ester), poly- methyl-prop Alkene acyloxybenzenesulfonic acids etc. have sulfonic macromolecule or polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic Acid, polyacrylamide yl carboxylic acid, polymethacryl carboxylic acid, poly- (2- acrylamide -2- methylpropane carboxylic acid), polyisoprene Carboxylic acid, polyacrylic acid etc. have the macromolecule of carboxyl.The homopolymer that can be these substances can also be wherein of more than two kinds total Polymers.
Among these polyanions, from the viewpoint of it can further improve electric conductivity, preferably there is sulfonic macromolecule, more It is preferred that polystyrolsulfon acid.
Aforementioned polyanion can be used alone a kind, can also be used in combination of two or more.
The matter average molecular weight of polyanion is preferably 20,000 or more 100 ten thousand hereinafter, more preferably 100,000 or more 50 ten thousand or less.Poly- yin The matter average molecular weight of ion is to measure elution time using gel permeation chromatography (GPC), is based on the polyphenyl as known to molecular weight The molecular weight for the quality criteria that the molecular weight that ethylene standard substance is previously obtained is found out relative to the calibration curve of elution time.
The content ratio of polyanion in conductive composite body is excellent relative to pi-conjugated 100 mass parts of electroconductive polymer The range of 1 mass parts or more, 1000 below the mass is selected as, more than more preferably 10 mass parts, 700 below the mass, into one Step is preferably 100 mass parts or more, 500 range below the mass.If the content ratio of polyanion aforementioned minimum value with On, then tend to enhance to the doping effect of pi-conjugated electroconductive polymer, electric conductivity becomes higher.On the other hand, if poly- yin from The content of son is in aforementioned upper limit value hereinafter, then can sufficiently contain pi-conjugated electroconductive polymer, thus ensuring that adequately conductive Property.
(tertiary ethylene carbonate polymer)
Tertiary ethylene carbonate polymer is the homopolymer of tertiary ethylene carbonate or is tertiary ethylene carbonate and can be with versatic acid second The copolymer of the other monomers of enester copolymerization.Herein, tertiary ethylene carbonate is the vinyl esters indicated by following chemical formula (1). The vinyl esters is the high monomer of hydrophobicity, and polymer obtained by the monomer polymerization is also the high substance of hydrophobicity.
In following chemical formula (1), R1, R2Respectively alkyl, R1、R2At least one of be the alkyl with branched structure.Separately Outside, R1Carbon atom number and R2The aggregate value of carbon atom number be preferably 4 or more, 7 hereinafter, more preferably 4 or more, 6 or less.
As composition R1、R2Alkyl, can enumerate: methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, sec-butyl, Isobutyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, 1,1- dimethylbutyl, 2- methyl amyl, 3- methylpent Base, 4- methyl amyl, 1- ethyl-butyl, 2- ethyl-butyl, 3- ethyl-butyl, 1- methyl-1-ethyl propyl.
In aforesaid alkyl, the alkyl with branched structure are as follows: isopropyl (1- Methylethyl), tert-butyl (1,1- dimethyl second Base), sec-butyl (1- methyl-propyl), isobutyl group (2- methyl-propyl), tertiary pentyl (1,1- dimethyl propyl), isopentyl (3- first Base butyl), sec-amyl (1- methyl butyl), 1,1- dimethylbutyl, 2- methyl amyl, 3- methyl amyl, 4- methyl amyl, 1- Ethyl-butyl, 2- ethyl-butyl, 3- ethyl-butyl, 1- methyl-1-ethyl propyl.
In addition, tertiary ethylene carbonate is the compound indicated by chemical formula (1), can be total carbon atom number is 9 or more, 11 or less Compound mixture.
[changing 1]
It as the other monomers that can be copolymerized with tertiary ethylene carbonate, such as can enumerate: vinyl acetate, vinyl alcohol, (first Base) alkyl acrylate, (methyl) acrylic acid, alkene, (methyl) acrylamide etc.." (methyl) acrylic acid " in this specification It is the general designation of acrylic acid and methacrylic acid.Aforementioned other monomers can be used alone a kind, can also be used in combination of two or more.
In aforementioned other monomers, from the copolymerization of easy and tertiary ethylene carbonate and adhesiveness, conductive layer of the conductive layer to plastic basis material Water resistance become higher viewpoint and set out, preferably vinyl acetate, vinyl alcohol, (methyl) alkyl acrylate, (methyl) third Olefin(e) acid, alkene.
It as (methyl) alkyl acrylate, such as can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2- methoxyl group second Ester, (methyl) glycidyl acrylate etc..
It as alkene, such as can enumerate: ethylene, propylene, 1- butylene etc..
As the concrete example of tertiary ethylene carbonate and the copolymer for the other monomers that can be copolymerized with tertiary ethylene carbonate, can arrange Lift: tertiary ethylene carbonate-vinyl acetate copolymer, tertiary ethylene carbonate-vinyl acetate-(methyl) alkyl acrylate are total Polymers, tertiary ethylene carbonate-(methyl) alkyl acrylate copolymer, tertiary ethylene carbonate-(methyl) alkyl acrylate- (methyl) acrylic copolymer, tertiary ethylene carbonate-vinyl-vinyl acetate copolymer etc..
In addition, tertiary ethylene carbonate polymer also may include the monomeric unit with acidic group.As acidic group, can enumerate: sulfonic group, Carboxyl, phosphate etc..When tertiary ethylene carbonate polymer includes the monomeric unit with acidic group and electroconductive polymer dispersion When liquid includes the acrylic resin containing glycidyl, since tertiary ethylene carbonate polymer and third containing glycidyl occurs The reaction of olefin(e) acid resin, therefore the water resistance of conductive layer and solvent resistance further increase.In addition, poly- in tertiary ethylene carbonate Object is closed comprising the monomeric unit with acidic group and in the case where having carried out hydrophilicity-imparting treatment to plastic basis material as described later, due to Tertiary ethylene carbonate is bonded directly to the surface of plastic basis material, therefore conductive layer further increases the bonding force of plastic basic unit.
As the monomer with acidic group, in addition to (methyl) acrylic acid, crotonic acid etc., work when can enumerate synthesis tertiary ethylene carbonate The monomer with acidic group generated for by-product.
Tertiary ethylene carbonate polymer includes the carboxylic acids such as versatic acid, acetic acid as field trash sometimes.Tertiary ethylene carbonate polymer Carboxylic acid value be preferably 5~30mgKOH/g, more preferably 5~20mgKOH/g.In addition, carboxylic acid value can be according in the present specification JIS K 0070 is measured.
The content of tertiary ethylene carbonate unit in tertiary ethylene carbonate polymer is relative to tertiary ethylene carbonate polymer Gross mass be preferably 10 mass % or more, 100 mass % hereinafter, more preferably 20 mass % or more, 90 mass % is hereinafter, into one Step is preferably 30 mass % or more, 70 mass % or less.If tertiary ethylene carbonate unit in tertiary ethylene carbonate polymer contains Amount is more than aforementioned minimum value, then conductive layer can further improve the adhesiveness and water resistance of plastic basic unit.On the other hand, If the tertiary ethylene carbonate unit in tertiary ethylene carbonate polymer content in aforementioned upper limit value hereinafter, if can make electric conductivity height Dispersibility in molecular dispersions is promoted.
The glass transition temperature of tertiary ethylene carbonate polymer is preferably 10 DEG C or more 100 DEG C hereinafter, more preferably 20 DEG C or more 80 DEG C or less.The glass transition temperature of tertiary ethylene carbonate polymer can be measured with differential scanning calorimeter.
If the glass transition temperature of tertiary ethylene carbonate polymer more than aforementioned minimum value, can further promote conductive layer Water resistance and solvent resistance, if in aforementioned upper limit value hereinafter, if conductive layer can be made sufficiently to mention the adhesiveness of plastic basic unit It rises.
The matter average molecular weight of tertiary ethylene carbonate polymer is preferably 1000 or more 1000000 hereinafter, more preferably 5000 Above 500000 hereinafter, further preferably 10000 or more 100000 or less.The matter average molecular weight of tertiary ethylene carbonate polymer For use gel permeation chromatography (GPC) measure elution time, based on the polystyrene standards matter as known to molecular weight it is preparatory The molecular weight for the quality criteria that obtained molecular weight is found out relative to the calibration curve of elution time.
If the matter average molecular weight of tertiary ethylene carbonate polymer more than aforementioned minimum value, can make conductive layer to plastic basic unit Adhesiveness is sufficiently promoted, if in aforementioned upper limit value hereinafter, if can make tertiary ethylene carbonate polymer electroconductive polymer disperse Dispersibility in liquid is promoted.
When obtaining tertiary ethylene carbonate polymer, use persulfate as polymerization initiator sometimes.In this case, The aqueous dispersions of tertiary ethylene carbonate polymer show acidity because of remaining sulfate ion sometimes.Becoming acid situation Under, preferably sulfuric acid is neutralized.If sulfuric acid is neutralized, it can make tertiary ethylene carbonate polymer in electroconductive polymer dispersion liquid Dispersibility promoted.That is, it is preferred that tertiary ethylene carbonate polymer does not include sulfuric acid as field trash.
It is preferably 4~9 according to the pH that JIS Z 8802:2011 is measured about tertiary ethylene carbonate polymer, more preferably 4.5 ~8.5.In addition, pH measurement is as follows.
1) sample 5g is weighed, 0.1g unit is accurate to.
2) distilled water 95ml is measured to 100ml beaker with graduated cylinder.PH meter is set in beaker, is put into rotor, while using magnetic agitation The hydrochloric acid of device stirring distillation waterside addition 0.01mol/L or the sodium hydrate aqueous solution of 0.01mol/L, after static 1 minute PH at 23 DEG C is adjusted to stablize 7.0.
3) sample is added to the beaker that joined the distilled water for being adjusted to pH7.0, obtains dispersion liquid.
4) it after five minutes with magnetic stirrer dispersion liquid, stops rotating, the pH after reading 1 minute.
The sulfuric acid for including in tertiary ethylene carbonate polymer can be neutralized using the addition of alkali cpd.
Alkali cpd can be inorganic base, any one in organic base.
It as inorganic alkali compound, such as can enumerate: sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium bicarbonate, bicarbonate Potassium, ammonium hydrogen carbonate etc..
It as organic base, can enumerate: primary amine, secondary amine, tertiary amine, quaternary ammonium salt, nitrogenous aromatic ring compounds.
It as primary amine, such as can enumerate: aniline, toluidines, benzylamine, ethanol amine etc..
It as secondary amine, such as can enumerate: diethanol amine, dimethylamine, diethylamine, di-n-propylamine, diphenylamines, dibenzylamine, dinaphthylamine etc..
It as tertiary amine, such as can enumerate: triethanolamine, trimethylamine, triethylamine, tripropyl amine (TPA), triphenylamine, tribenzylamine, three naphthylamines etc..
It as quaternary ammonium salt, such as can enumerate: tetramethyl ammonium, tetraethyl ammonium salt, tetrapropyl ammonium salt, tetraphenyl ammonium salt, tetrabenzyl Ammonium salt, four naphthalene ammonium salts etc..は hydroxide ion can be enumerated as the anion pairs of with ammonium.
It as nitrogenous aromatic ring compounds, such as can enumerate: aniline, benzylamine, pyrroles, imidazoles, 2-methylimidazole, 2- propyl miaow Azoles, N- methylimidazole, 1- (2- ethoxy) imidazoles, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 1- benzyl -2- methyl Imidazoles, 1- 1-cyanoethyl-2-methylimidazole, 1- cyanoethyl -2-ethyl-4-methylimidazole, 2- phenyl -4,5- bishydroxymethyl miaow Azoles, 1- acetyl imidazole, 2- aminobenzimidazole, 2- amino -1- tolimidazole, 2- hydroxybenzimidazole, 2- (2- pyridine Base) benzimidazole, pyridine etc..
Aforementioned base compounds can be used alone a kind, can also be used in combination of two or more.
The content of tertiary ethylene carbonate polymer in electroconductive polymer dispersion liquid is relative to 100 matter of conductive composite body Amount part be preferably 10 mass parts or more 100000 below the mass, it is more than more preferably 50 mass parts that 50000 below the mass, into One step be preferably 100 mass parts or more 10000 below the mass.If the content of tertiary ethylene carbonate polymer is in aforementioned minimum value More than, then conductive layer can be made further to promote the adhesiveness of plastic basic unit, if in aforementioned upper limit value hereinafter, if can prevent because leading The decline of electric conductivity caused by the content of electrical complex is reduced.
(adhesive ingredients)
As the concrete example of adhesive ingredients, such as adhesive resin can be enumerated such as: polyester resin, acrylic resin, asphalt mixtures modified by epoxy resin Rouge, oxetane resin, polyurethane resin, polyimide resin, melamine resin, silicone resin, vinyl acetate tree Rouge etc..
In addition, adhesive ingredients can also be the monomer or oligomer to form aforementioned binder resin.When forming conductive layer, it can pass through It polymerize aforementioned monomer or aforementioned oligomer to form adhesive resin.
Aforementioned adhesion agent ingredient can be used alone a kind, can also be used in combination of two or more.
Among aforementioned adhesion agent ingredient, further increased from the water resistance of conductive layer, mechanical properties become good sight Point sets out, preferred polyester resin.
Polyester resin can have acidic group.Polyester resin (hereinafter referred to as " polyester resin (1) ") with acidic group is dicarboxylic acid component It is the polyester resin with the alkali metal salt of acidic group (sulfonic group, carboxyl, phosphate etc.) with the condensation polymer of diol component.Due to Polyester resin (1) polarity is larger, therefore water dispersible is excellent, even if can also be stable in water without using emulsifier, stabilizer Dispersion.
It as foregoing dicarboxylic acids' ingredient, can enumerate: phthalic acid, terephthalic acid (TPA), dimethyl terephthalate (DMT), isophthalic two Formic acid, dimethyl isophthalate, 2,5- dimethyl terephthalic acid, 2,6- naphthalenedicarboxylic acid, biphenyl dicarboxylic acid, phthalic acid Equal aromatic dicarboxylic acids, the aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, decanedioic acid and dodecanedicarboxylic acid, with And alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid etc..Foregoing dicarboxylic acids can be used alone a kind, can also be used in combination of two or more.
Foregoing dicarboxylic acids' ingredient is preferably comprised neutralized with sulfonic group by alkali metal obtained by sulfonate alkali metal salt form substituent group (-SO3-X+, X is alkali metal ion) dicarboxylic acids.
The dicarboxylic acids of substituent group with sulfonate alkali metal salt form is to be formed with the sulfonic group in sulfonic dicarboxylic acids The compound of alkali metal salt.
It as with sulfonic dicarboxylic acids, can enumerate: sulfonic group terephthalic acid (TPA), 5- sulfonic group M-phthalic acid, 4- sulfonic acid Base M-phthalic acid, 4- sulfonic group naphthalene -2,7- dicarboxylic acids or their derivative etc..As alkali metal, sodium, potassium etc. can be enumerated.
As the dicarboxylic acids of the substituent group with sulfonate alkali metal salt form, preferably the sodium salt of 5- sulfonic group M-phthalic acid and its spread out Biology.
Among dicarboxylic acid component, as the dicarboxylic acids in addition to the dicarboxylic acids of the substituent group with sulfonate alkali metal salt form at Point, optimization aromatic dicarboxylic acids, more preferable terephthalic acid (TPA), M-phthalic acid.The aromatic proton and hydrophobicity of aromatic dicarboxylic acid Plastics compatibility it is big, in addition, hydrolytic resistance is excellent.
The content ratio of the dicarboxylic acids of substituent group with sulfonate alkali metal salt form is preferably 6 in whole dicarboxylic acid components Mole 20 moles of % of % or more are hereinafter, 18 moles of % or less of more preferably 10 moles of % or more.If having sulfonate alkali metal salt form Substituent group dicarboxylic acids content ratio more than aforementioned minimum value, can inhibit the reduction of the solvent resistance of conductive layer, if Aforementioned upper limit value is hereinafter, the water resistance of conductive layer becomes higher.
As the diol component for forming polyester resin (1), can enumerate: diethylene glycol (DEG), carbon atom number are 2 or more 8 rouge below Fat race or carbon atom number are 6 or more 12 alicyclic diols below etc..As carbon atom number 2 be above 8 aliphatic below or Carbon atom number is the concrete example of 6 or more 12 alicyclic diols below, can be enumerated: ethylene glycol, 1,3-PD, 1,2- the third two Alcohol, neopentyl glycol, 1,4- butanediol, 1,4 cyclohexane dimethanol, 1,3- cyclohexanedimethanol, 1,2- cyclohexanedimethanol, 1, 6- hexylene glycol, terephthalyl alcohol, triethylene glycol etc..Foregoing glycols ingredient can be used alone a kind, can also be used in combination of two or more.
From the viewpoint of diol component promotes water resistance and solvent resistance further, diethylene glycol (DEG) is preferably comprised.
The number-average molecular weight of polyester resin (1) is preferably 2,000 or more 30, and 000 hereinafter, more preferably 2, and 500 or more 25, 000 or less.The number-average molecular weight of polyester resin (1) is elution time to be measured using gel permeation chromatography (GPC), based on by dividing Son measures the quantity that the molecular weight that known polystyrene standards matter is previously obtained is found out relative to the calibration curve of elution time The molecular weight of benchmark.
If the number-average molecular weight of polyester resin (1), more than aforementioned minimum value, the water resistance of polyester resin (1) further mentions Height, if in aforementioned upper limit value hereinafter, if the water dispersible of polyester resin (1) further increase.
It as the manufacturing method of polyester resin (1), is not particularly limited, such as can enumerate: making dicarboxylic acid component and glycol Ingredient carries out esterification or ester exchange reaction at 130 DEG C or more 200 DEG C or less, then at reduced pressure conditions and at 200 DEG C or more 250 DEG C or less carry out polycondensation reaction method.It, can as catalysts used in the manufacturing method in aforementioned polyester resin (1) It enumerates: the acetic acid metal salt such as zinc acetate, manganese acetate, the metal oxides such as antimony oxide, germanium oxide, titanium compound etc..
Obtained polyester resin (1), which also may be added to that, becomes aqueous dispersion in water.About the aqueous dispersion of polyester resin (1), by Increase in solid component concentration, becomes to be not easy to obtain uniform dispersion, therefore polymer solids constituent concentration is preferably 30 mass % Below.
In addition, as adhesive ingredients, also improve from improve the water resistance of conductive layer while its solvent resistance in terms of Consider, preferably containing the acrylic resin of glycidyl.
If supposition contains the acrylic resin containing glycidyl as adhesive ingredients, due to forming friendship in the conductive layer It is coupled structure, therefore water resistance and solvent resistance are promoted.
In addition, can further improve conductive layer if containing the acrylic resin containing glycidyl as adhesive ingredients To the adhesiveness of plastic basic unit.Its reason is still not clear, but is presumably due to the acrylic resin containing glycidyl and is clipped in Between plastic basis material and the polyanion for constituting conductive composite body, thus hydrophilic polyanion is relative to hydrophobic modeling Material substrate is immobilized.Thus it is speculated that being glued by the conductive layer that water-based electroconductive polymer dispersion liquid is formed to plastic basis material Conjunction property is promoted.
Particularly, in the case where having carried out the plastic basis material of hydrophilicity-imparting treatment using surface, the acrylic acid containing glycidyl It is that resin is easy to react with the hydrophilic radical (hydroxyl, carboxyl etc.) in plastic basis material Surface Creation.It is therefore contemplated that plastic basis material Adhesiveness further increase.
Acrylic resin containing glycidyl is only by the free-radical polymerised unsaturated monomer containing glycidyl Homopolymer that unit is constituted or with containing glycidyl free-radical polymerised insatiable hunger monomeric unit and can be total with aforementioned monomer The copolymer of other poly- free-radical polymerised unsaturated monomer units.
Acrylic resin containing glycidyl can be used alone a kind, can also be used in combination of two or more.
It as the free-radical polymerised unsaturated monomer containing glycidyl, can enumerate: glycidyl acrylate, methyl The glycidol ethers such as glycidyl acrylate, allyl glycidyl ether, among them, preferably Glycidyl methacrylate is sweet Grease.Free-radical polymerised unsaturated monomer containing glycidyl can be used alone a kind, can also be used in combination of two or more.
The free-radical polymerised unsaturated monomer list containing glycidyl in acrylic resin containing glycidyl The content ratio of member is preferably 10 mass % or more, 100 mass % hereinafter, more preferably relative to whole 100 mass % of monomeric unit For 20 mass % or more, 100 mass % or less.If containing the freedom of glycidyl in the acrylic resin containing glycidyl The content ratio of base polymerism unsaturated monomer unit then can further promote the electric conductivity by the method more than 10 mass % The water resistance and solvent resistance for the conductive layer that high molecular dispersion liquid is formed.
As can be copolymerized with the free-radical polymerised unsaturated monomer containing glycidyl other are free-radical polymerised not Be saturated monomer, can enumerate: vinyl esters, esters of unsaturated carboxylic acids (alkyl acrylate, alkyl methacrylate etc.) are unsaturated Carboxylic acid amide (acrylamide, Methacrylamide etc.), unsaturated nitrile (acrylonitrile etc.), unsaturated carboxylic acid (acrylic acid, methyl-prop Olefin(e) acid etc.), olefinic monomer.Other free-radical polymerised unsaturated monomers can be used alone a kind, can also be used in combination of two or more.
As other free-radical polymerised unsaturated monomers, it is preferable to use propylene from the viewpoint of further increasing water resistance The unsaturated carboxylic acid monomers such as acid, methacrylic acid.
The content ratio of unsaturated carboxylic acid monomer unit in acrylic resin containing glycidyl is relative to whole monomers 100 mass % of unit is preferably 5 mass % or more, 20 mass % or less.If insatiable hunger in the acrylic resin containing glycidyl Content ratio with carboxylic monomer unit is more than aforementioned minimum value, then the water resistance and solvent resistance that can make conductive layer are into one Step is promoted, if in aforementioned upper limit value hereinafter, if can inhibit liquid gelled over time and storage stability reduces.
It as the manufacturing method of the acrylic resin containing glycidyl, is not particularly limited, such as using lotion Acrylic resin of the polymerization manufacture containing glycidyl.
In the manufacture using the acrylic resin containing glycidyl of emulsion polymerization, such as ion is put into reactive tank Exchanged water, polymerization initiator, surfactant then put into ion exchange water and surfactant, investment monomer to dropping bath After preparing monomer emulsion, make emulsion free-radical polymerization by the way that aforementioned monomer emulsion droplet is added to reactive tank. Reaction temperature be preferably set to 60 DEG C or more 100 DEG C hereinafter, the reaction time be preferably set to 10 hours 4 hours or more or less.
As surfactant used in emulsion polymerization, anionic surfactant, non-ionic reactive table can be used It is one kind or two or more in face activating agent and non-reactive surfactant.
As polymerization initiator used in emulsion polymerization, general free-radical polymerised initiator can be enumerated, such as: persulfuric acid The oil-solubles mistake such as the water-soluble peroxides such as potassium, ammonium persulfate, hydrogen peroxide or benzoyl peroxide, tert-butyl hydroperoxide Azo-compounds such as oxide or azodiisobutyronitrile etc..
In the case where manufacturing the acrylic resin containing glycidyl using emulsion polymerization, it is as containing glycidyl Acrylic resin lotion obtain.
The content of adhesive ingredients in electroconductive polymer dispersion liquid is preferred relative to 100 mass parts of conductive composite body Below the mass for more than 100 mass parts 10000, more than more preferably 100 mass parts 5000 below the mass, further preferably Below the mass for more than 100 mass parts 1000.If the content of adhesive ingredients more than aforementioned minimum value, can make conductive layer Strength enhancing, if in aforementioned upper limit value hereinafter, if can prevent the content because of conductive composite body from reducing caused by electric conductivity It reduces.
(decentralized medium)
As the decentralized medium used in this mode, can enumerate: water, organic solvent, water and organic solvent mixed liquor.
It as organic solvent, such as can enumerate: alcohols solvent, ether solvent, ketones solvent, esters solvent, aromatic hydrocarbon solvent Deng.
It as alcohols solvent, such as can enumerate: methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, 2- methyl-2-propanol, n-butyl alcohol, 2- fourth Alcohol, 2- methyl-1-propyl alcohol, allyl alcohol, propylene glycol monomethyl ether, glycol monoethyl ether etc..
It as ether solvent, such as can enumerate: diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, propylene glycol dialkyl ether etc..
It as ketones solvent, such as can enumerate: metacetone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl Ketone, methyl Isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol etc..
It as esters solvent, such as can enumerate: ethyl acetate, propyl acetate, butyl acetate etc..
It as aromatic hydrocarbon solvent, such as can enumerate: benzene,toluene,xylene, ethylbenzene, propyl benzene, isopropylbenzene etc..
Aforementioned organic solvents can be used alone a kind, can also be used in combination of two or more.
Among aforementioned organic solvents, from the dispersion that can further improve conductive composite body and tertiary ethylene carbonate polymer From the perspective of property, preferred methanol.
As described later, since conductive composite body is obtained as aqueous dispersion, preferably in electroconductive polymer Decentralized medium is also aqueous in dispersion liquid.Water phase is for constituting the gross masses of the whole decentralized media of electroconductive polymer dispersion liquid Content ratio be preferably 50 mass % or more, 100 mass % hereinafter, more preferably 80 mass % or more, 100 mass % hereinafter, into One step is preferably 90 mass % or more, 100 mass % or less.Decentralized medium can also all water.
(highly conductive agent)
In order to promote electric conductivity further, electroconductive polymer dispersion liquid also may include highly conductive agent.
Herein, pi-conjugated electroconductive polymer above-mentioned, polyanion, tertiary ethylene carbonate polymer and adhesive ingredients be not It is classified as highly conductive agent.
Highly conductive agent be preferably selected from by carbohydrate, nitrogenous aromatic ring compounds, the compound with 2 or more hydroxyls, Compound with 1 or more hydroxyl and 1 or more carboxyl, the compound with amide groups, with the chemical combination of imide At least one kind of compound for the group that object, lactam compound, the compound with glycidyl form.
Highly conductive agent contained by electroconductive polymer dispersion liquid can be a kind, can also be two or more.
The content ratio of highly conductive agent in electroconductive polymer dispersion liquid is preferred relative to 100 mass parts of conductive composite body Below the mass for more than 1 mass parts 10000, more than more preferably 10 mass parts 5000 below the mass, further preferably It is more than 100 mass parts that 2500 below the mass.If the content ratio of highly conductive agent is more than aforementioned minimum value, because highly conductive Electric conductivity caused by the addition of agent promoted effect give full play to, if in aforementioned upper limit value hereinafter, if can prevent pi-conjugated electric conductivity The reduction of electric conductivity caused by polymer concentration reduces.
(other additives)
It also may include other well known additives in electroconductive polymer dispersion liquid.
As additive, as long as effect of the invention can be obtained, it is not particularly limited, such as usable surfactant, Inorganic conductive agent, defoaming agent, coupling agent, antioxidant, ultraviolet absorbing agent etc..Wherein, additive includes except above-mentioned pi-conjugated Chemical combination other than electroconductive polymer, polyanion, tertiary ethylene carbonate polymer, adhesive ingredients and highly conductive agent Object.
As surfactant, the surfactant of non-ionic, anionic, cationic can be enumerated, but is stablized from saving From the perspective of property, preferably non-ionic surfactant.In addition, the polymerization species table such as polyvinylpyrrolidone can also be added Face activating agent.
As inorganic conductive agent, metal ion class, conductive carbon etc. can be enumerated.In addition, metal ion can be by keeping metal salt molten It is generated in Xie Yushui.
As defoaming agent, silicone resin, dimethyl silicone polymer, silicone oil etc. can be enumerated.
As coupling agent, the silane coupling agent etc. with epoxy group, vinyl or amino can be enumerated.
As antioxidant, phenol antioxidant, amine antioxidants, phosphorus antioxidants, sulphur class antioxidant, sugar can be enumerated Class etc..
It as ultraviolet absorbing agent, can enumerate: Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorbent, water Poplar esters of gallic acid ultraviolet absorbing agent, cyanoacrylate ultraviolet absorbent, oxanilide class ultraviolet absorbing agent, hindered amine Class ultraviolet absorbing agent, benzoates ultraviolet absorbing agent etc..
In the case where electroconductive polymer dispersion liquid contains above-mentioned additive, content ratio is appropriate according to the type of additive It determines, such as the range of 0.001 mass parts or more 5 below the mass can be set as relative to 100 mass parts of conductive composite body.
(manufacturing method of electroconductive polymer dispersion liquid)
The method of electroconductive polymer dispersion liquid as manufacture the method, such as can enumerate: in the aqueous solution of polyanion, Make to form the monomer of pi-conjugated electroconductive polymer progress chemical oxidising polymerisation, the aqueous dispersions of conductive composite body is prepared, to this The method of tertiary ethylene carbonate polymer is added in aqueous dispersions.In making electroconductive polymer dispersion liquid containing adhesive at Point, in the case where highly conductive agent, other additives etc., added in Xiang Qianshu aqueous dispersions.
In addition, commercially available product can also be used in the aqueous dispersions of conductive composite body.
Since the hydrophobicity of tertiary ethylene carbonate polymer is high, so if directly adding then in electroconductive polymer dispersion liquid Dispersibility reduce.Therefore, in order to improve the dispersibility in electroconductive polymer dispersion liquid, preferably in advance by versatic acid ethylene Ester is made as lotion to add.
In afore mentioned chemical oxidation polymerization, well known catalyst can be applied.Such as catalyst and oxidant can be used.Make For catalyst, such as the transistion metal compounds such as iron chloride, ferric sulfate, ferric nitrate, copper chloride can be enumerated etc..As oxidant, Such as the persulfates such as ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate can be enumerated.Oxidant can make the catalyst being reduced return to original The state of oxidation come.
As the content for the conductive composite body for including in electroconductive polymer aqueous dispersions, disperse relative to electroconductive polymer The gross mass of liquid is preferably 0.1 mass % or more, 10 mass % hereinafter, preferably 0.3 mass % or more, 5 mass % is hereinafter, more excellent It is selected as 0.5 mass % or more, 4 mass % or less.
(function and effect)
Since the electroconductive polymer dispersion liquid of the method includes the conduction containing pi-conjugated electroconductive polymer and polyanion Sex camplex, therefore conductive conductive layer is become by the layer that said conductive high molecular dispersion liquid is formed.
In the past, electric conductivity was assigned using surface of the surfactant to plastic basis material sometimes.
Particularly, it when assigning electric conductivity to the high polyolefin-based resins substrate of hydrophobicity, is often assigned using surfactant Electric conductivity.But the Humidity Dependence height of the electric conductivity obtained using surfactant, the conductive sexual orientation under low-humidity environment In reduction.In contrast, using pi-conjugated electroconductive polymer performance electric conductivity the method in, electric conductivity do not have humidity according to Lai Xing, the electric conductivity that can be played stably.
The previous electroconductive polymer dispersion liquid comprising pi-conjugated electroconductive polymer, due to more because of its manufacturing method For aqueous dispersion, thus it is low to the wetability of plastic basis material.Therefore, the conductive layer pair formed by electroconductive polymer dispersion liquid The adhesiveness of plastic basis material is low, wherein especially low to the adhesiveness for the substrate being made of polyolefin-based resins.In addition, by water system Electroconductive polymer dispersion liquid formed conductive layer water resistance it is low.
But the electroconductive polymer dispersion liquid of the method is due to comprising tertiary ethylene carbonate polymer, to plastic basis material Wetability promoted.Therefore, the conductive layer to be formed can be made to promote the adhesiveness of plastic basis material.It is special even with hydrophobicity The adhesiveness of high olefin-based resin substrate, the conductive layer formed by the electroconductive polymer dispersion liquid of the method is also high.Speculate It is high to the compatibility of plastic basis material since tertiary ethylene carbonate polymer has the high alkyl of hydrophobicity, thus to plastic basis material, Especially the wetability of polyolefin-based resins substrate is promoted, the adhesiveness of conductive layer is promoted.In addition, thus it is speculated that tertiary ethylene carbonate The compatibility of polymer and conductive composite body is high.
In addition, the hydrophobicity due to tertiary ethylene carbonate polymer is high, can make to be dispersed by the electroconductive polymer of the method The water resistance for the conductive layer that liquid is formed is promoted.
Therefore, it according to the electroconductive polymer dispersion liquid of the method, can easily form to the adhesiveness of plastic basis material and water-fast The excellent conductive layer of property.
Particularly, thus it is speculated that there is the monomeric unit containing acidic group in tertiary ethylene carbonate polymer and plastic basis material has carried out hydrophiling In the case where processing, the anionic group of polyanion becomes catalyst, sends out tertiary ethylene carbonate polymer and plastic basis material Life is reacted and is bonded.If tertiary ethylene carbonate polymer is bonded with plastic basis material, conductive layer to the adhesiveness of plastic basis material with And the water resistance of conductive layer further increases.
In addition, the electroconductive polymer dispersion liquid of the method is mainly coated on film substrate as described later, but can also be coated on The plastic basis material of three-dimensional shape in addition to film substrate.
< conductive membrane >
Fig. 1 is the cross-sectional view for indicating an example of conductive membrane of the invention.
The conductive membrane 1 of one embodiment of the present invention has: film substrate 2, and by said conductive high molecular dispersion liquid shape At the conductive layer 3 on an at least side surface for aforementioned film substrate 2.
The conductive membrane of the method can use directly as packaging material, can also as described later as antistatic property container at Type material and use.The packaging material of conductive membrane comprising the method, conductive layer play the function as antistatic layer, Such as paying for dust can be prevented.It is therefore possible to prevent the commodity of packaging caused by being attached on packaging material because of dust (such as are eaten Product etc.) appearance damage.
Aforementioned film substrate is plastic film substrate.
It as the film substrate resin of composition plastic film, such as can enumerate: polyolefin-based resins, ethane-acetic acid ethyenyl ester Copolymer resins, ethylene methyl methacrylate copolymer resins, polystyrene, polyvinyl chloride, polyvinyl alcohol, poly terephthalic acid Glycol ester, polyethylene naphthalate, polyacrylate, polycarbonate, gathers inclined difluoro at polybutylene terephthalate (PBT) Ethylene, polyarylate, styrenic elastomer, polyester elastomer, polyether sulfone, polyetherimide, polyether-ether-ketone, polyphenylene sulfide, Polyimides, Triafol T, cellulose acetate propionate etc..As polyolefin-based resins, can enumerate: polyethylene, polypropylene, Ethylene-alpha-olefin copolymer resins, propylene-alpha olefin copolymer resins etc..
The method is suitable among plastic film thin using the higher film of polyolefin resin of hydrophobicity, particularly polypropylene The case where film.In this mode, even the extra high film substrate of hydrophobicity, also can be improved the adhesiveness of conductive layer.
In addition, film substrate can be the film substrate being not stretched, the film substrate being stretched can also be.
In addition, can also be hydrophilic to form carboxyl, hydroxyl etc. by carrying out aftermentioned hydrophilicity-imparting treatment on the surface of film substrate Group.
As the average thickness of aforementioned film substrate, preferably 10 μm or more 500 μm hereinafter, more preferably 20 μm or more 200 μm or less.If the average thickness of film substrate does not allow easy fracture more than aforementioned minimum value, if aforementioned upper limit value with Under, then it can ensure that the sufficient flexibility as film.
Component in this specification with a thickness of being measured with micrometer to the thickness at any 10, be averaged to the measured value It is worth obtained by value.
Conductive layer in the method includes: the conductive composite body containing pi-conjugated electroconductive polymer and polyanion, And tertiary ethylene carbonate polymer.
In the case where in the electroconductive polymer dispersion liquid used when manufacturing conductive membrane including adhesive ingredients, conductive layer Include adhesive resin.
As the average thickness of aforesaid conductive layer, preferably 10nm or more 20000nm hereinafter, more preferably 20nm or more 10000nm is hereinafter, further preferably 30nm or more 5000nm or less.If the average thickness of conductive layer aforementioned minimum value with On, then can give full play to high conductivity, if in aforementioned upper limit value hereinafter, if can easily form conductive layer.
With resistrivity meter (Mitsubishi, Co., Ltd. chemical analysis (Mitsubishi Chemical Analytech) system, Hiresta), the sheet resistance value of the conductive layer measured under conditions of applied voltage is 10V is preferably 5.0 × 105~5.0 × 109Ω/□.In addition, Ω/ refers to Ω/sq..
The conductive membrane of the method can be by applying said conductive high score on an at least side surface for film substrate Sub- dispersion liquid, be allowed to drying form conductive layer to manufacture.
It is preferred that before applying electroconductive polymer dispersion liquid, to film substrate implement Corona discharge Treatment, corona treatment, The hydrophilicity-imparting treatments such as flame treatment form hydrophilic radical (hydroxyl, carboxyl, carbonyl etc.) on the surface of film substrate.Work as film When substrate has carried out hydrophilicity-imparting treatment, the adhesiveness of conductive layer can be made further to be promoted.Among hydrophilicity-imparting treatment, from can be easy From the perspective of ground makes the surface hydrophilic of film substrate, preferred Corona discharge Treatment.
As the method in film substrate coating electroconductive polymer dispersion liquid, such as can apply: using slit coater, Flush coater, roll coater, curtain stream coating machine, spin coater, metering bar coater, reverse coating machine, coincide at gravure coater Formula coating machine, jet flow coating machine, rod coater, air knife coater, scraper coating machine (knife coater), scraping blade The coating method of the coating machines such as formula coating machine (bladecoater), cast coat machine, silk screen coating machine, the dipping such as dipping (dip) Method etc..
As the drying means being coated with after electroconductive polymer dispersion liquid, heat drying, vacuum drying etc. can be enumerated.It is leading Electrical high molecular dispersion liquid includes at least one of aforementioned polyester resin (1) and acrylic resin containing glycidyl In the case where, from the viewpoint of promoting reaction, preferred heat drying.As heat drying, such as Hot-blast Heating, red can be used The usual ways such as outside line heating.
In the case where application heat drying, heating temperature is suitably set according to the decentralized medium used, but usually at 50 DEG C Above 150 DEG C of ranges below, preferably 60 DEG C or more 130 DEG C are hereinafter, more preferably in 70 DEG C or more 120 DEG C of ranges below It is interior.Herein, heating temperature is the set temperature of drying device.
In addition, drying time is preferably 5 minutes or more from the viewpoint of sufficiently removing decentralized medium.
< antistatic property container >
Fig. 2 is the cross-sectional view for indicating an example of antistatic property container of the invention.
The antistatic property container 10 of one embodiment of the present invention includes the formed body of said conductive film 1.Resisting for the method is quiet Electrical container plays antistatic property by the inclusion of the conductive layer of conductive composite body.
The shape of the antistatic property container of the method is not particularly limited, as long as the article that can accommodate conveying or storage can be formed Space.The article that antistatic property container about the method is accommodated, electronic component etc. may due to static discharge by The component of destruction is suitable.As the antistatic property container for accommodating electronic component, it can enumerate and be formed with multiple receiving ministrys of electronics industry The container of the banding or sheet of the recess portion of part.It as electronic component, such as can enumerate: IC, LSI, capacitor etc..
Antistatic property container is manufactured and making said conductive film forming.As forming method, such as can be using true The empty method of forming, pressure empty shaping method, extrusion forming method etc..Among these forming methods, from can made both easily and inexpensively form receiving From the perspective of the recess portion of article, preferred vacuum forming.
The condition of vacuum forming can be adjusted to the condition of desired recess portion easy to form.As vacuum forming condition, can enumerate Forming temperature, vacuum degree etc..
Forming temperature is preferably greater than 110 DEG C, is preferably set to 120 DEG C or more 180 DEG C or less.Herein, when forming temperature refers to molding Conductive membrane surface temperature.If forming temperature is more than 110 DEG C, easily conductive membrane can be made to form.Another party Face, if forming temperature be set as aforementioned upper limit value hereinafter, if can prevent conductive membrane from heat deterioration occurring at the time of molding.
[embodiment]
(Production Example 1)
The sodium styrene sulfonate that 206g is dissolved in the ion exchange water of 1000ml, dripped through 20 minutes while stirring at 80 DEG C It is dissolved in the ammonium persulfate oxidizing agent solution of the 1.14g in the water of 10ml in advance, stirs the solution 12 hours.
Into the obtained solution containing sodium styrene sulfonate, addition is diluted to the sulfuric acid 1000ml of 10 mass %, utilizes ultrafiltration The about 1000ml solution for removing the solution containing polystyrolsulfon acid adds the ion exchange water of 2000ml, benefit into Liquid Residue About 2000ml solution is removed with ultrafiltration.It is repeated 3 times above-mentioned ultrafiltration.Further, molten to obtained polystyrolsulfon acid The ion exchange water that about 2000ml is added in liquid removes the solution of about 2000ml using ultrafiltration.It is repeated 3 times the ultrafiltration.
The water in obtained solution is removed under reduced pressure, obtains the polystyrolsulfon acid of colorless solid.
(Production Example 2)
By the 3,4- ethyldioxythiophene of 14.2g and the polystyrolsulfon acid of 36.7g is made to be dissolved in the ion exchange of 2000ml Solution obtained from water mixes at 20 DEG C.
Thus obtained mixed solution is maintained at 20 DEG C, the ion friendship for being dissolved in 200ml is slowly added while stirring The oxidation catalyst solution of the ammonium persulfate of the 29.64g in water and the ferric sulfate of 8.0g is changed, stirring is allowed to react for 3 hours.
The ion exchange water of 2000ml is added into obtained reaction solution, removes about 2000ml solution using ultrafiltration.It is repeated 3 times The operation.
Then, the sulfuric acid for being diluted to 10 mass % of 200ml and the ion exchange water of 2000ml are added into obtained solution, The solution of about 2000ml is removed using ultrafiltration, the ion exchange water of 2000ml is added thereto, is removed about using ultrafiltration 2000ml solution.It is repeated 3 times the operation.
Further, the ion exchange water of 2000ml is added into obtained solution, removes the molten of about 2000ml using ultrafiltration Liquid.It is repeated 5 times the operation, the polystyrolsulfon acid for obtaining 1.2% adulterates poly- (3,4- ethyldioxythiophene) (PEDOT-PSS Aqueous dispersions) solution.In addition, PSS is 75 mass % relative to the content of PEDOT-PSS solid component.
(Production Example 3)
18 mass parts of ion exchange water, anionic surfactant (Sanyo Chemical are put into beaker Industries, Ltd. system, ELEMINOL RS-3000,50 mass % of effective component) 3 mass parts.Thereafter, in side stirring beaker Side puts into 40 mass parts of glycidyl methacrylate, prepares monomer emulsion.
Then, ion exchange is put into the four-hole boiling flask for having condenser, monomer dropping liquid funnel, thermometer and blender 37.5 mass parts of water, anionic surfactant (Sanyo Chemical Industries, Ltd. system, ELEMINOL RS- 3000) 1 mass parts, 0.5 mass parts of potassium peroxydisulfate.Thereafter, it carries out nitrogen displacement while stirring in flask, begins to warm up, reach After 75 DEG C, dripped aforementioned monomer emulsion for 4 hours.Fluid temperature is also maintained 75 DEG C or more 85 DEG C after terminating by dropping liquid Thus range below promotes reaction, is cooled down after 4 hours since terminating dropping liquid.After cooling, further it is added Ion exchange water obtains the acrylic resin aqueous dispersion containing glycidyl of 25 mass % of non-volatile content.
(embodiment 1)
Into the PEDOT-PSS aqueous dispersions 25g obtained by Production Example 2, water 25g, tertiary ethylene carbonate-vinyl acetate are added Copolymer emulsion (Showa Denko K. K's system, Polysol OLX-7879, solid component concentration: 46 mass %, pH1.7, glass Glass transition temperature: 0 DEG C, matter average molecular weight: 200,000 or more 50 ten thousand hereinafter, carboxylic acid value: 15mgKOH/g is denoted in the table as " Polysol OLX-7879 ") 50g, it mixes, obtains electroconductive polymer dispersion liquid.
Obtained electroconductive polymer dispersion liquid has been implemented poly- the third of sided corona treatment coated on surface with No.4 metering bar coater On alkene film, it is allowed to 1 minute dry at 85 DEG C, forms conductive layer, obtain conductive membrane.
(embodiment 2)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7879 and product, solid component concentration: 46 mass %, pH6.2, neutralizer: ammonia, glass transition temperature: 0 DEG C, the equal molecule of matter Amount: 200,000 or more 50 ten thousand hereinafter, carboxylic acid value: 15mgKOH/g is denoted in the table as " Polysol OLX-7879 neutralization ") other than, with Embodiment 1 equally operates, and obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, similarly to Example 1 Ground obtains conductive membrane.
(embodiment 3)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to 7878, pH1.8, glass transition temperature: 60 DEG C, matter average molecular weight: 200,000 or more 50 ten thousand hereinafter, carboxylic acid value: 15mgKOH/g, Solid component concentration: 46 mass % are denoted in the table as " Polysol OLX-7878 ") other than, it operates, obtains similarly to Example 1 To electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, conductive membrane is obtained similarly to Example 1.
(embodiment 4)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7878 and product, pH5.9, neutralizer: ammonia, glass transition temperature: 60 DEG C, matter average molecular weight: 200,000 or more 50 ten thousand hereinafter, carboxylic Acid value: 15mgKOH/g, solid component concentration: 46 mass % are denoted in the table as " Polysol OLX-7878 neutralization ") other than, with Embodiment 1 equally operates, and obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, similarly to Example 1 Ground obtains conductive membrane.
(embodiment 5)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- The more 5g of quantitative change 7879), further addition polyester aqueous solution (Goo Chemical Co., Ltd., Plus coat Z-690, 25 mass % of solid component concentration) other than 45g, operates obtain electroconductive polymer dispersion liquid similarly to Example 1.Use this Electroconductive polymer dispersion liquid, obtains conductive membrane similarly to Example 1.
(embodiment 6)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7879 and product) other than, operate similarly to Example 5, obtain electroconductive polymer dispersion liquid.Use the electroconductive polymer point Dispersion liquid obtains conductive membrane similarly to Example 1.
(embodiment 7)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to 7878) it other than, operates similarly to Example 5, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, Conductive membrane is obtained similarly to Example 1.
(embodiment 8)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7878 and product) other than, operate similarly to Example 5, obtain electroconductive polymer dispersion liquid.Use the electroconductive polymer point Dispersion liquid obtains conductive membrane similarly to Example 1.
(embodiment 9)
In addition to by polyester aqueous solution (Goo Chemical Co., Ltd., Plus coat Z-690,25 matter of solid component concentration Amount %) it is changed to polyester aqueous solution (Goo Chemical Co., Ltd., Plus coatRZ-105,25 matter of solid component concentration Measure %) other than, it operates similarly to Example 7, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, Conductive membrane is obtained similarly to Example 1.
(embodiment 10)
In addition to by polyester aqueous solution (Goo Chemical Co., Ltd., Plus coat Z-690,25 matter of solid component concentration Measure %) being changed to water-dispersion type copolyester aqueous solution, (Co., Ltd., Bironal 1245, solid component concentration 30 spin in Japan Quality %) other than, it operates similarly to Example 7, obtains electroconductive polymer dispersion liquid.Dispersed using the electroconductive polymer Liquid obtains conductive membrane similarly to Example 1.
(embodiment 11)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) quantitative change more 5g, mixed liquor (the high terebinth for also adding acrylic resin and polyester resin containing glycidyl Co. Ltd. system, PESRESIN A-647GEX, aqueous dispersion, 20 mass % of solid component concentration) other than 45g, with embodiment 1 Same operation, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, obtain similarly to Example 1 Conductive membrane.
(embodiment 12)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7879 and product) other than, operate similarly to Example 11, obtain electroconductive polymer dispersion liquid.Use the electroconductive polymer Dispersion liquid obtains conductive membrane similarly to Example 1.
(embodiment 13)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to 7878) it other than, operates similarly to Example 11, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, Conductive membrane is obtained similarly to Example 1.
(embodiment 14)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7878 and product) other than, operate similarly to Example 11, obtain electroconductive polymer dispersion liquid.Use the electroconductive polymer Dispersion liquid obtains conductive membrane similarly to Example 1.
(embodiment 15)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) quantitative change more 5g, the acrylic resin aqueous dispersion containing glycidyl obtained by Production Example 3 is further added It other than 45g, operates similarly to Example 1, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, with Embodiment 1 gets similarly conductive membrane.
(embodiment 16)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7879 and product) other than, operate similarly to Example 15, obtain electroconductive polymer dispersion liquid.Use the electroconductive polymer Dispersion liquid obtains conductive membrane similarly to Example 1.
(embodiment 17)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to 7878) it other than, operates similarly to Example 15, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, Conductive membrane is obtained similarly to Example 1.
(embodiment 18)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7878 and product) other than, operate similarly to Example 15, obtain electroconductive polymer dispersion liquid.Use the electroconductive polymer Dispersion liquid obtains conductive membrane similarly to Example 1.
(embodiment 19)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) quantitative change more 10g, the acrylic resin water dispersion containing glycidyl obtained by Production Example 3 is further added It other than body 40g, operates similarly to Example 1, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, Conductive membrane is obtained similarly to Example 1.
(embodiment 20)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7879 and product) other than, operate similarly to Example 19, obtain electroconductive polymer dispersion liquid.Use the electroconductive polymer Dispersion liquid obtains conductive membrane similarly to Example 1.
(embodiment 21)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to 7878) it other than, operates similarly to Example 19, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, Conductive membrane is obtained similarly to Example 1.
(embodiment 22)
In addition to by tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- 7879) tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX- are changed to In 7878 and product) other than, operate similarly to Example 19, obtain electroconductive polymer dispersion liquid.Use the electroconductive polymer Dispersion liquid obtains conductive membrane similarly to Example 1.
(comparative example 1)
In addition to not adding tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa into PEDOT-PSS aqueous dispersions 25g Electrician's Co. Ltd. system, Polysol OLX-7879) 50g, replacing increases to the additive amount of water other than 75g, with implementation Example 1 equally operates, and obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, similarly to Example 1 To conductive membrane.
(comparative example 2)
In addition to not adding tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX-7879) 50g, replace and add polyester aqueous solution (Goo Chemical Co., Ltd., Plus coat Z-690) 50g In addition, it operates similarly to Example 1, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, with implementation Example 1 gets similarly conductive membrane.
(comparative example 3)
In addition to not adding tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX-7879) 50g, replace and add polyester aqueous solution (Goo Chemical Co., Ltd., Plus coat RZ-105) 50g In addition, it operates similarly to Example 1, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, with implementation Example 1 gets similarly conductive membrane.
(comparative example 4)
In addition to not adding tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX-7879) 50g, replace and add water-dispersion type copolyester aqueous solution (Co., Ltd., Bironal 1245 are spun by Japan) It other than 50g, operates similarly to Example 1, obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, with Embodiment 1 gets similarly conductive membrane.
(comparative example 5)
In addition to not adding tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX-7879) mixed liquor (the high pine tar of 50g, acrylic resin and polyester resin of the addition containing glycidyl that replace Rouge Co. Ltd. system, PESRESIN A-647GEX) other than 50g, operate similarly to Example 1, obtain electroconductive polymer dispersion Liquid.Using the electroconductive polymer dispersion liquid, conductive membrane is obtained similarly to Example 1.
(comparative example 6)
In addition to not adding tertiary ethylene carbonate-vinyl acetate copolymer lotion (Showa Denko K. K's system, Polysol OLX-7879) other than 50g, the acrylic resin 50g containing glycidyl for adding and being obtained by Production Example 3 that replaces, with Embodiment 1 equally operates, and obtains electroconductive polymer dispersion liquid.Using the electroconductive polymer dispersion liquid, similarly to Example 1 Ground obtains conductive membrane.
< evaluates >
[sheet resistance value]
To the conductive layer of the conductive membrane of each example, resistrivity meter (Mitsubishi, Co., Ltd. chemical analysis (Mitsubishi is used Chemical Analytech) system, Hiresta) in the condition measurement sheet resistance value of applied voltage 10V.Sheet resistance value Measurement result is shown in table 1, table 2.
[adhesiveness]
In the conductive membrane of each example, after the surface mount adhesive tape of conductive layer, which is removed.Pass through Visually the presence or absence of the removing of conductive layer of observation at this time, evaluates adhesiveness by following benchmark.Evaluation result is shown in table 1, Table 2.
A: the removing nothing of conductive layer, adhesiveness are high.
B: the removing of conductive layer has, and adhesiveness is low.
[water resistance]
In the conductive membrane of each example, on the surface of conductive layer, by aqueous non-woven fabrics in 100g/cm2Pressure under rub 10 back and forth.The presence or absence of the removing of conductive layer at this time is observed by visual observation, and water resistance is evaluated by following benchmark.Evaluation As a result shown in table 1, table 2.
A: the removing nothing of conductive layer, water resistance are high.
B: conductive layer generates panels with multiple site damage, and water resistance is slightly lower.
C: the removing of conductive layer has, and water resistance is low.
[solvent resistance]
In the conductive membrane of each example, on the surface of conductive layer, by the non-woven fabrics containing isopropanol in 100g/cm2Pressure under Friction 10 is back and forth.The presence or absence of the removing of conductive layer at this time is observed by visual observation, and solvent resistance is commented by following benchmark Valence.Evaluation result is shown in table 1, table 2.
A: the removing nothing of conductive layer, solvent resistant are high.
B: conductive layer generates panels with multiple site damage, and solvent resistance is slightly lower.
C: the removing of conductive layer has, and solvent resistance is low.
[table 1]
[table 2]
By simultaneously comprising conductive composite body and tertiary ethylene carbonate-vinyl acetate copolymer electroconductive polymer Dispersion liquid is formed in the Examples 1 to 22 of conductive layer, and the sheet resistance value of conductive layer is small, and electric conductivity is high.In addition, for embodiment 1~22 conductive membrane, conductive layer are high to the adhesiveness of film substrate, and the water resistance of conductive layer is also high.
Among previous embodiment, in the electroconductive polymer point by further including the acrylic resin containing glycidyl Dispersion liquid is formed in the embodiment 11~22 of conductive layer, and the solvent resistance of conductive layer is also excellent.
In contrast, dispersing by the electroconductive polymer comprising conductive composite body but not comprising tertiary ethylene carbonate polymer Liquid is formed in the comparative example 1~6 of conductive layer, and conductive layer is all low to both the adhesiveness of film substrate, the water resistance of conductive layer.Separately Outside, the solvent resistance of the conductive membrane about comparative example 1~6, conductive layer is low.
Include adhesive ingredients in electroconductive polymer dispersion liquid in comparative example 2~6, but the adhesiveness of conductive layer and Water resistance is low.It follows that even if adhesive ingredients is added into conductive composite body, the adhesiveness and water resistance of conductive layer It is not promoted, by the way that tertiary ethylene carbonate polymer is added, the adhesiveness and water resistance of conductive layer get a promotion.
(embodiment 23)
Using have upper mold and have recess portion lower die vacuum forming machine by the conductive membrane of embodiment 13 carry out vacuum at Type.Specifically, conductive membrane is configured between upper mold and lower die, in utilization in the state that upper mold and lower die are opened The heater of mould is heated when measuring film surface temperature.
After film surface temperature reaches 150 DEG C, increase towards upper mold lower die, pushes and support to conductive membrane, in the state It directly vacuumizes down, is kept for 20 seconds from lower die side.Thereafter, 40 DEG C are cooled to, lower die is declined, takes out formed body.
In addition, formed body has the cylindric recess portion that opening portion is the circle of diameter 100mm, depth is 30mm.In addition, vacuum at Stretching ratio when type is set as 3 times.
For the formed body obtained using vacuum forming, also measure sheet resistance value, and to the adhesiveness of conductive layer, water resistance with And solvent resistance is evaluated.As a result shown in table 1.
For obtained formed body, electric conductivity, conductive layer are to the adhesiveness of film substrate, the water resistance of conductive layer and resistance to molten Any one in agent is all high.Such formed body can be suitable as accommodating the antistatic property container of electronic component etc. and making With.

Claims (20)

1. a kind of electroconductive polymer dispersion liquid, contains:
Conductive composite body, it includes pi-conjugated electroconductive polymer and polyanions；
Tertiary ethylene carbonate polymer；And
Decentralized medium.
2. electroconductive polymer dispersion liquid according to claim 1, wherein
The tertiary ethylene carbonate polymer includes from the monomeric unit of tertiary ethylene carbonate and from vinyl acetate The monomeric unit of ester.
3. electroconductive polymer dispersion liquid according to claim 1, wherein
The pH according to JIS Z 8802:2011 measurement of the tertiary ethylene carbonate polymer is 4~9.
4. electroconductive polymer dispersion liquid according to claim 1, wherein
The decentralized medium contains water.
5. electroconductive polymer dispersion liquid according to claim 1, wherein
The pi-conjugated electroconductive polymer is poly- (3,4- ethyldioxythiophene).
6. electroconductive polymer dispersion liquid according to claim 1, wherein
The polyanion is polystyrolsulfon acid.
7. electroconductive polymer dispersion liquid according to claim 1, wherein
The electroconductive polymer dispersion liquid also contains adhesive ingredients.
8. electroconductive polymer dispersion liquid according to claim 7, wherein
Described adhesive ingredient is polyester resin.
9. electroconductive polymer dispersion liquid according to claim 7, wherein
Described adhesive ingredient is the acrylic resin containing glycidyl.
10. a kind of conductive membrane, has:
Film substrate；And
The conductive layer formed on the surface of the film substrate by electroconductive polymer dispersion liquid described in claim 1.
11. conductive membrane according to claim 10, wherein
The film substrate includes polyolefin-based resins.
12. conductive membrane according to claim 11, wherein
The polyolefin-based resins are acrylic resin.
13. a kind of manufacturing method of conductive membrane comprising apply right on the surface of at least side of film substrate and want Electroconductive polymer dispersion liquid described in asking 1 is simultaneously allowed to the dry process for forming conductive layer.
14. the manufacturing method of conductive membrane according to claim 13, wherein
The film substrate includes polyolefin-based resins.
15. the manufacturing method of conductive membrane according to claim 14, wherein
The polyolefin-based resins are acrylic resin.
16. the manufacturing method of conductive membrane according to claim 13, wherein
The film substrate has hydrophilic radical on the surface.
17. the manufacturing method of conductive membrane according to claim 16, wherein
The film substrate is obtained and carrying out Corona discharge Treatment to surface.
18. a kind of antistatic property container, it includes make according to claim 1 conductive membrane described in any one of 0~12 at Formed body obtained from type.
19. a kind of manufacturing method of antistatic property container, includes
The process of the manufacturing method manufacture conductive membrane of conductive membrane described in any one of 3~17 according to claim 1； And
Make the molding process of the conductive membrane.
20. the manufacturing method of antistatic property container according to claim 19, wherein
The process for making the molding process of conductive membrane make the conductive membrane vacuum forming.
CN201810885353.2A 2017-08-08 2018-08-06 Electroconductive polymer dispersion liquid, conductive membrane and its manufacturing method and antistatic property container and its manufacturing method Pending CN109385189A (en)

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